Production of phosphates



Dec; 16, 19 41. c. R. MCCULLOUGH 2,266,328

PRODUCTION OF PHOSPHATES Filed July 1, 1959 2 Sheets-Sheet l INVENTOR c. McCULLOUGH ATTOR NEY Dec. 16, 1941. c. R. MCCUL LOU G H 2,266,3

" PRODUCTION ,OF PHOSPHATES Filed July 1, 1939 2 Sheets-Sheet 2 ATTORNEY Patented Dec. 16, 1941 PRODUCTION OF PHQSPHATES @Campbell R. McCullough, Anniston, Ala., assignor to Monsanto Chemical Company, a corporation I of Delaware Application July '1,' 1939, Serial No. 282,634;

' 50mins.- ,(91. 23-106) The-present. invention relates to a method for the production of phosphates byprocesses in which phosphorus is oxidized and the oxidation products thereof are combined with compounds including salts having a replaceable anion.; .Ac-

cording to the present invention I may produce either acid, neutral, or basic salts of. phosphoric acid. a r An object of the present invention is to provide a method and apparatus by which the heat generated by the combustion of phosphorus is first efiiciently utilized for the production of salts of phosphorus.

.A further object of this invention is the provision of a method and apparatus by which the heat absorbing .surfaces of phosphorus-burning chambers may be greatly augmented.

My invention will be described by reference to the drawings illustratingmethods and appa ratus by .which my invention may be practiced.

In the drawings Figure I shows a rotary burning chamber 10 rotatably mounted upon tires -ll androllersl2.i

The rotary burning chamber [0, is equipped with end plates l3 and-14, each provided with central openings l5 and I6, Admission and outlet headers I1 and "I8 are provided adjacent theopenings l5 and I6. Outlet header l8 connects with mist filter 19, in which ,is supported a layer of fine coke or other packing material 20 suitable for filtering out phosphoric acid mist. Suction is applied to the mist filter l9 by means of fan 2|. A supply of water22 may be applied to the top of the filter bed 20, serving to dilute the acid collected upon the filtering surfaces. In place of water, a dilute solution .of phosphate of soda or other alkali may beintroduced by means of 22. Acid or sodium phosphate solution collected in filter l9 flows out by means of pipe 23 and may either-be used as collected or may be returned to the. rotary 'fumace by pipe 25, as indicated on the :drawings;

In operation molten yellowphosphorus and air are introduced into one end or the. furnace, for example, by means of header 'll located ad jacent opening l5. =Water vapor or steam may also be introduced together with the air used for combustion. I I

A supply of salt may be introduced through an opening in header l'l, said salt being conveniently conveyed'and projected into the interio'r "of the furnace 10' by means ofascrew through furnace l0 concurrently. By suitable change, countercurrent operation may be practiced. Discharge of molten salt generated within' furnace l0 is effected through a discharge header l8 provided adjacent opening "5.; 7

During operation of the process combustion of yellow phosphorus takes place withinfurnace l0,l.which.is' maintained at a suitable speed of rotation, and the combustion products react with the solid salt which is simultaneously fed into the furnace, causing the volatile anion thereof to be displaced and forming amolten phosphorus salt. When'required for the reaction, steam or water-maybe introduced, either separately or together with the air provided for maintaining combustion .of phosphorus. I

- During operation the .temperature within furnace ,lll reaches'anincandescent temperature by combustion ofthe phosphorus with the air introduced,. and the oxidation products react with salt to produce molten phosphorus compounds which normally collect in a pool at the lower part of the furnace. By virtue of the rotation of the furnace themolten salt is carried upwardly upon the interiorsurfacesof the said furnace; .Cooling fluid; is applied to the exterior of the shell, of furnace l0,;said fluid being applied in1quantities so'as. to mantain adjacenttheinterior of said metal shell a layer. of-solid phosphorus-containing salts.. By virtue. of. the solid layer of, salt maintained upon the interior surfaces of the said furnace, corrosion of the metal furnace is com pletely prevented from taking place.. 3 g

When rotating the .furnace at relatively slow 'speeds'jthepool of'molten phosphorussalts is maintained substantially at the. lowerpart of thefurnace and only, a small amount ofmolten salt is carried upwardlyby the movin Walls of the furnace... At increasingly higher speeds of rotationa greater amount is thus carriedupwardlywithin the furnace, andImay so increase the speed of rotation of thejfurnacethat the normalpool at. the lower part of. the. furnace will. completely. disappear because all of I the moltensalt has been carriedupwardly'and maintained against said furnacewalls by centrifugal force. The latter condition has been designated conveyor 'o'r "an air blast. With therarrange ment shown the air and phosphorus, or the com -bu'stion products thereof; 'are'ima'de' flow 55 as a centrifugally maintained liquid lining.

, Prior to the development of. the last-named centrifugallining, however, I have found that within certain criticalrotational speeds I obtain .a phenomenon in which the molten salt leaves .the. wallof the furnace before the highest point 'is'reached; and falls downwardly through the furnace; interion, This. condition I have designated as rain, because of the fact that the atmosphere within the furnace is filled with droplets and streams of molten salt. When this condition exists an enormously greater surface of molten salt is presented to the gases and vapors within the furnace atmosphere. This greatly increased surface materially increases the absorption of heat and also phosphorus oxidation and hydration products thereof by the molten salts. As an example, I have found that the absorption of phosphorus anhydride may be increased from, say, 50-60% of the phosphorus burned when using ordinary slow-speed rotational velocities of the furnace, to as much as 90-95 per cent when using the r'ain condition of operation. The absorption o'fheat by the molten salt is also increased.

The efiect above described is shown igraph dition of "rain by providing the interior surface of the drum with blocks or projections fastened thereto. In such cases the solid and the liquid layer of salt adjacent the interior of the furnace wall assumes roughly the configuration of said wall, providing the optimum condition for production of rain.

In my co-pending application, Serial No. 255,574, which was filed Feb. 10, 1939, which application describes and claims a' method and apparatus for producing acids of phosphorus, I

have described and illustrated various types of furnaces for obtaining the effect described.

By means of the herein disclosed process I am able to, produce the various metal phosphates, such as metaphosphate, tetrasodium pyrophosphate, "and the various polyphosphates.

\ By the use f superheated or oxygen enriched air ically in Figures II to V inclusive of the draW- ings which are taken along section 'A-AOf" Figurel. V

Figure 11 shows .the condition resulting from what I term slow-speed .operation, and indicates that a fairly quiet pool ofmoltensalt remains within the furnace with a substantially horizontal surface. y

Figure III shOWs conditionsobtainin in the furnace at a somewhat fasterspeed of turning, and indicates that the pool of molten solt is be-v ing carried upwardly by the rising furnace wall so that the'level of the pool is no longer horizontal,

Figure IV shows conditions existing in the furnace at a still higher speed of revolution than that shown in Figure III. In this condition the' molten salt within the furnace leaves the wall before the highest point is reachedand thereafter falls freely downwardly through the furnace atmosphere. This is the condition which. :I designate as rain, because the atmosphere within the, fur,-

nace is filled with very. many droplets and streams of molten salt.

Figure V shows the condition existing in the furnace at astill higher speed than that illus:

trated in FigureIV. Underthe conditions illus- 2:,

trated by FigureV the furnaceis turning at what has beendesignated as high-speed or centrifugal speed. Under this condition the molten salt is maintained as a continuous liquid .film or layer upon the interior of thefurnace wall, and the atmosphere within the furnace is relatively free of the droplets and streams of salt illustrated by Figure IV. 1

'Since the conditions illustrated by the drawings, Figures II to V inclusive, are dependent '55 upon the diameter of the furnace and the viscosityof the molten salt, which viscosity isfurther dependent upon the character and temperature of said salt, it is impossible to numerically state the speed'at which the various phenomena Figures VI to -VIII inclusive illustrate various non-cylindrical drum cross-sections suitablefor I may-produce trisodium phosphate or other salts havinga high melting point. I may also produce the co'rrespo'ndlng potassium salts- It ,is also contemplated "that thejpro'duction of :other metallic :phosphates, :such as phosphates of calcium, aluminum, magnesium,.-lead and zinc, may be produced: bythe herein described process. Addition compounds of phosphorua such as calcium metaphosphate may be made by reaction of tricalcium phosphate or phosphate rock withoxidation products of phosphorus. The raw materials which are supplied in solid or liquidfo'rm to the furnace may be-determin'ed by the-product which is to be made. For example, I may feed to said furnace sodium chloride, sodium carbonate, sodium hydroxide, (potassium chloride, carbonate, or hydroxide or, whenip'rodu'cing "calcium phosphates, Imay -feed the various "calcium .salts, such as calcium chloride, sulfate, phosphate, etc.

When operating under fthe conditions described, I may. iobtainan i'absorption. of from %-'to 95% of the phosphorus burned directly -in-thel molten =salt within the furnace. '1 accordingly so proportion the amount of .fphosphorus burned and the salt fed tolgive the product-of. composition desired; Several examples will" serve to illustrate lmy inventions:

' Ex mple I;-'Production of tetra sodium 'Iniafurnace having a. metal shell 6 feet long and '24 inches, in diameter, externally cooled and revolving at 210 R. -P.,M., at whichspeedI obtain the rain phenomenon mentioned above, I feed .7100 pounds -of phosphorus an hour, 156 *cu. ftraof air :;a minute, and 308 'pound'sof soda ash an-h'our. .I obtain an "estimated exit gas temperature within said furnace of 11001200 C. which is well above the melting point of tetrasodium pyro.phosphate (980 C.);.and therefrom discharge-a productat the rateofqfififi pounds. F n hour The absorption obtained is of the phosphorus burned. Theipr'oduct will ordinarily analyze as follows: 7

.A product of thisanalysis is better than 99% *Namzoq. I 1 j,

The product leaving the furnace, amolten state, may-be cooled-by achilling device,;or may be. cooled :and disintegrated byr'a blast of air or steamto "giveL-a .finely divided product." 1 f The phosphorus" pentoxide-containing gases -(-containingi the EPz'Os unabsorbediin the furnace) pass out of; saidzfumace and are cooled-by spray my purpose. It is also possible to obtain the con- 725 ing: them: directlyzwith-water of dilute sodium EXAMPLE 2.-Production of sodium hewa-metaphosphate In the same furnace described in Example I, I feed phosphorus at the rate of 100 pounds an hour, soda ash at the rate of 144 pounds an hour, and withdraw sodium metaphosphate at the discharge of the furnace at the rate of 280 pounds an hour. The absorption obtained is 85% of the phosphorus burned. Since the process yields directly a molten metaphosphate at the V discharge of the furnace, I then quickly cool the molten product by allowing it to fall directly upon a chilled plate or upon chill rolls to produce flakes, or the product may be cooled and disintegrated by a blast of air. By thus quickly cooling the molten product I am enabled to produce what is commonly referred to as the hexa-metaphosphate of sodium.

EXAMPLE 3.Production of alkali metal polyphosphates When it is desired to produce any of the various polyphosphates of the alkali metals by my process, I adjust the supply of alkali metal salt and the phosphorus absorbed to produce the desired stoichiometric composition. The production of the various sodium polyphosphates, for example, will take place according to the following equations: a

(a) Sodium triphosphate 5Na2CO3 6P +7 O2=2Na5P3O1o+ 5CO2 (b) Sodium tetraphosphate 3Na2CO3 +4P +502=NasP4013 +3CO2 (6) Sodium decaphosphate GNazCOa 10F 12 O2=Na12P1oO31+ M302 ((1) Sodium hexerohexaphosphate I 4Na2CO3+ P+7 /gO2=NasP6Oi9-{4CO2 I am enabled by my process to produce the above mentioned polyphosphates or compositions approximating these polyphosphates by a simple, direct process without the intermediate production of other phosphates. contemplates the use of air as the oxidizing medium; however, oxygen-enriched air or other oxygen-containing gases may be used.

I may use generally for the production of the sodium phosphates, sodium salts or compounds which may be considered as combinations of NazO or Na and a replaceable or volatile anion, that is, said anion being replaceable or volatile at the temperature of the reaction. The temperature of the reaction should be maintained above the melting point of thephosphate, or polyphosphate, produced. 7

What I claim is:

1. A method for producing a salt of phosphorus which comprises providing a layer of said salt of phosphorus upon the interior of the metal shell of an exterior-1y cooled rotating furnace, establishing an incandescent temperature within said furnace by supplying thereto hot products of combustion of phosphorus, supplying to said The above process furnace a metal compoundv reactive with .said products of combustion, to produce therewith a molten phosphorus containing salt and rotating said furnace at a rate, suchthat the said molten salt leaves thefurnace wall before the highest point thereof'is reached andv falls down through the furnace atmosphereras droplets and streams of said. salt, wherebythe absorption of phosphorus combustion-products by said salt is ma-- terially increased,-said-rate of rotation being less than that required to maintain a centrifugal lining of said salt.

2. A method for producing tretasodium pyrophosphate which comprises providing a layer of said pyrophosphate upon the interior of the metal shell of an exteriorly cooled rotating furnace, establishing an incandescent temperature within said furnace by supplying thereto hot products of combustion of phosphorus, supplying to said furnace soda ash to produce said tetrasodium pyrophosphate in the molten state, rotat- 7 ing said furnace at a rate such that said molten pyrophosphate leaves the furnace wall before the highest point is reached, and falls down through the furnace atmosphere as droplets and streams of said molten salt, whereby the absorption of said phosphorus combustion products by said salt is increased to as much as to said rate of rotation being less than that required to maintain a centrifugal lining of said salt.

3. A method for producing sodium metaphosphate, which comprisesproviding a layer of said phosphate upon the interior of the metal shell of an exteriorly cooled rotating furnace, establishing an incandescent temperature within said furnace by supplying thereto hot phosphorus combustion products, supplying to said furnace a sodium salt having a replaceable anion to produce said metaphosphate in the molten state, and rotating said furnace at a rate such that said molten metaphosphate leaves the furnace wall before the highest point is reached and falls down through the furnace atmosphere as droplets and streams of molten salt, whereby the absorbing surface of the molten salt is increased to the extent that up to 90% to 95% of said phosphorus combustion products are absorbed by said molten salt, said rate of rotation being less than that required to maintain said molten salt as a centrifugal lining upon said furnace interior.

4. A methodfor producing a sodium polyphosphate compound which comprises providing a layer of said compound upon the interior of the metal shell of an exteriorly cooled rotating furnace, establishing an incandescent temperature within said furnace by supplying to said furnace hot phosphorus combustion products, supplying to said furnace a sodium salt having a replaceable anion to produce said polyphosphate in the molten state and rotating said furnace at a rate less than that required to maintain said molten polyphosphate as a centrifugal lining, but said rate being such that said molten polyphosphate leaves the furnace wall before the highest point encountered during rotation is reached and falls down through the furnace atmosphere as droplets and streams of molten salt, whereby the absorbing surface of the molten salt is increased to the extent that up to 90% to 95% of said phosphorus combustion products are absorbed in said molten polyphosphate.

lining, but said rate "being :such that said molten :10

polyphosphate, leaves the :furnace wall before the highest point encountered during rotation is reached and falls down through the furnace atmosphere as droplets and streams of molten salt, whereby the absorbing surface of the molten salt .is increased to the extent that up to 90% to 95% of said phosphorus combustion products are absorbed in. said molten polyphosphate.

CANEBELL R. MCCULLOUGH. 

